CN113430828A

CN113430828A - Fiber product and preparation method thereof

Info

Publication number: CN113430828A
Application number: CN202110697016.2A
Authority: CN
Inventors: 张洪玉; 王毅
Original assignee: Tsinghua University
Current assignee: AFFILIATED HOSPITAL OF HEBEI UNIVERSITY; Tsinghua University
Priority date: 2021-06-23
Filing date: 2021-06-23
Publication date: 2021-09-24
Anticipated expiration: 2041-06-23
Also published as: CN113430828B; WO2022267841A1

Abstract

The invention discloses a fiber product, which comprises a polymer fiber and a zwitterionic polymer combined on the subsurface and the surface of the polymer fiber, wherein the polymer fiber and the zwitterionic polymer form a double-network interpenetrating structure, and the subsurface of the polymer fiber is a position with the distance from the outer surface of the polymer fiber being in a nanoscale size. The invention also discloses a preparation method of the fiber product, which comprises the following steps: mixing an electrostatic spinning compound and an initiator in a solvent to obtain an electrostatic spinning solution, wherein the mass ratio of the electrostatic spinning compound to the initiator in the electrostatic spinning solution is 100: (0.5 to 5); carrying out electrostatic spinning on the electrostatic spinning solution to obtain polymer fibers with initiators distributed on the subsurface; infiltrating polymer fibers with initiators distributed on the sub-surfaces with a zwitterionic compound solution; and (3) carrying out polymerization reaction of initiating the zwitterionic compound on the polymer fiber soaked with the zwitterionic compound solution under the initiation condition of an initiator.

Description

Fiber product and preparation method thereof

Technical Field

The invention relates to the technical field of fiber materials, in particular to a fiber product and a preparation method thereof.

Background

At present, the ultra-smooth modification of the surface of the material has received great attention, but no reports have been made on the ultra-smooth modification of the nanofiber membrane, particularly on the simple and stable ultra-smooth modification technology.

At present, the literature reports a method for constructing a functional coating on the surface of a solid medical device, such as the surface of a ceramic material, a metal material and the like, but the method for constructing the functional coating on the surface of a porous nano biological material, namely polymer nano fiber, without damaging the structure of the porous nano biological material is not reported. There are a few prior arts in which the functional compound is physically bonded to the polymer fiber by immersing the polymer fiber in a functional compound solution, but the inventors have found that this method not only destroys the structure of the polymer fiber itself, but also has a problem in that the functional compound is not firmly bonded to the polymer fiber.

Disclosure of Invention

In view of the above, it is necessary to provide a fiber product and a method for producing the same, which are directed to the problem that the surface modification of porous nanobubbles is lack of a stable and simple method.

One of the objects of the present invention is to provide a fibrous article comprising a polymer fiber and a zwitterionic polymer bonded to a subsurface of the polymer fiber and a surface of the polymer fiber, the polymer fiber and the zwitterionic polymer forming a dual-network interpenetrating structure, the subsurface of the polymer fiber being at a nano-scale distance from an outer surface of the polymer fiber.

In some of these embodiments, the polymer fibers have diameters on the nanometer or micrometer scale.

In some of these embodiments, the fibrous article is a web or a mat.

In some of these embodiments, the material of the polymeric fibers is selected from any one or more of the following electrospinnable compounds or polymers thereof: dextran, chitosan, polyvinylpyridine, cellulose ether, hydrolyzed polyacrylamide, polyacrylate, polycarboxylate, polyethylene oxide, polyethyleneimine, polyacrylic acid, polymethacrylic acid, hydroxypropylcellulose, cellulose acetate, cellulose nitrate, algin salt, pullulan, xanthan gum, polyurethane polystyrene, polymethacrylate, polyvinylidene fluoride, perfluoroalkoxy, fluorinated ethylene propylene, polytetrafluoroethylene, polyacrylonitrile, nylon, polycarbonate, polyethylene terephthalate, polyester, polyamide, polyamic acid, polyimide, polylactic acid, polyglycolic acid, polyvinyl chloride, polycaprolactone, polyaniline.

In some of these embodiments, the zwitterionic polymer is polymerized from one or more of 2-methacryloyloxyethyl phosphorylcholine, 3- [ [2- (methacryloyloxy) ethyl ] dimethyl ammonium ] propionate, 3- [ N, N-dimethyl- [2- (2-methylprop-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonic acid inner salt, and the base betaine.

It is another object of the present invention to provide a method for preparing a fibrous article of any of the above embodiments, comprising the steps of:

mixing an electrostatic spinning compound and an initiator in a solvent to obtain an electrostatic spinning solution, wherein the mass ratio of the electrostatic spinning compound to the initiator in the electrostatic spinning solution is 100: (0.5 to 5);

carrying out electrostatic spinning on the electrostatic spinning solution to obtain polymer fibers with the initiators distributed on the sub-surfaces;

infiltrating the polymer fiber with the initiator distributed on the subsurface by using a zwitterionic compound solution;

and (3) carrying out polymerization reaction of initiating the zwitterionic compound on the polymer fiber soaked with the zwitterionic compound solution under the initiation condition of the initiator.

In some of these embodiments, the initiator is selected from photopolymerization initiators, and the initiation conditions are ultraviolet irradiation.

In some of the embodiments, the photopolymerization initiator is selected from any one or more of benzoin alkyl ether-based initiators, benzophenone-based initiators, aromatic ketone-based initiators, aromatic ketal-based initiators, thioxanthone-based initiators, benzil-based initiators, benzoin-based initiators, α -ketol-based compounds, aromatic sulfonyl chloride-based compounds, photoactive oxime-based compounds, camphorquinone-based compounds, halogenated ketone-based compounds, acylphosphine oxide-based compounds, and acylphosphonate-based compounds; and/or, the photopolymerization initiator is selected from any one or more of IRGACURE 184, IRGACURE 127, DAROCUR 1173, IRGACURE 2959, IRGACURE 500, IRGACURE 369, IRGACURE 907, IRGACURE 651, IRGACURE 250, IRGACURE 819 and LUCIRIN TPO.

In some of these embodiments, the electrospinnable compound is selected from polylactic acid, the initiator is selected from IRGACURE 2959, and the mass ratio of the polylactic acid to the IRGACURE 2959 in the electrospinning solution is 100: (0.8 to 1.2).

In some of these embodiments, the parameter conditions for electrospinning are: the voltage is 18kV to 22kV, the receiving distance is 17cm to 19cm, and the solution advancing speed is 5.5mL/h to 6.5 mL/h.

The invention adopts an electrostatic spinning method to ensure that an initiator is automatically distributed on the subsurface of a single polymer fiber obtained by electrostatic spinning, and then the polymerization reaction of a zwitterionic compound is initiated under the initiation condition of a proper initiator, so that the zwitterionic polymer is inserted on the subsurface of the polymer fiber, and the two components form a subsurface dual-network interpenetrating structure. The results show that the method not only does not damage the size structure of the polymer fiber, but also enables the zwitterionic polymer to be firmly bonded on the polymer fiber through a spatial structure. The fiber product prepared by the method keeps the micro-nano size of the polymer of electrostatic spinning, endows the polymer fiber with the functions of lubricating and preventing tissue adhesion, and provides a foundation for the medical application of the polymer fiber with the micro-nano size.

Drawings

FIG. 1A is a photograph of a coated fibrous membrane electrode according to one embodiment of the present invention;

FIG. 1B is an enlarged view of FIG. 1A;

FIG. 1C is a photograph of a coated fibrous membrane electrode according to one embodiment of the present invention;

FIG. 1D is an enlarged view of FIG. 1C;

FIG. 1E is an XPS plot of a fiber film without a coating according to one embodiment of the present invention;

FIG. 1F is an XPS plot of a coated fiber film in accordance with an embodiment of the present invention;

FIG. 2A is a photograph of an uncoated fibrous membrane mirror according to a comparative example of the present invention;

FIG. 2B is an enlarged view of FIG. 2A;

FIG. 2C is a photograph of a coated fibrous membrane electrode of a comparative example of the present invention;

FIG. 2D is an enlarged view of FIG. 2C;

FIG. 2E is an XPS plot of an uncoated fiber film of a control example of the present invention;

FIG. 2F is an XPS plot of a coated fiber film of a control example of the present invention;

FIG. 3A is a graph showing tissue adhesion in mice without a fibrous membrane according to a control example of the present invention;

FIG. 3B shows the non-adherent condition of the mouse tissue with the coated fibrous membrane according to one embodiment of the present invention.

Detailed Description

To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.

Other than as shown in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients, physical and chemical properties, and so forth used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the foregoing specification and attached claims are approximations that can be suitably varied by those skilled in the art in seeking to obtain the desired properties utilizing the teachings disclosed herein. The use of numerical ranges by endpoints includes all numbers within that range and any range within that range, for example, 1 to 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4, and 5, and the like.

The term PDLLA, racemic polylactic acid, is much less crystalline than without racemization and therefore degrades more rapidly.

The term I-2959, the only U.S. FDA approved free radical polymerization initiator that can be used in humans.

The term post-surgical adhesions: a common complication following surgery is manifested as fibrous bands resulting from excessive healing between tissue surfaces.

The term UV, ultraviolet reaction, generally emits at a wavelength around 365 nm.

The term electrospinning is a manufacturing technique that utilizes a high-voltage electrostatic field to process a polymer solution into a micro-nano scale fiber structure.

The term subsurface, the interior of the material closest to the outer surface, is typically only on a nanometer scale, e.g., 0-1000 nm, 0-100 nm, etc. Can be 0 to 1nm, such as 0.001nm, 0.01nm, 0.1nm, 0.5nm, 1nm, from the outer surface. Can be 1-10 nm, such as 2nm, 4nm, 6nm, 8nm, 10nm, away from the outer surface. Can be 10-100 nm, such as 20nm, 40nm, 60nm, 80nm, 100nm, away from the outer surface. Can be 100-1000 nm, such as 200nm, 400nm, 600nm, 800nm, from the outer surface.

One of the objects of the present invention is to provide a fibrous article comprising a polymer fiber and a zwitterionic polymer bonded to a subsurface of the polymer fiber and a surface of the polymer fiber, the polymer fiber and the zwitterionic polymer forming a dual-network interpenetrating structure. The polymer fibers form a first network structure and the zwitterionic polymer forms a second network structure. The zwitterionic polymer is bonded to the polymer fibers through the subsurface and surface of the first network structure. The polymer fibers are bonded to the zwitterionic polymer through the subsurface and surface of the second network structure.

In the fiber product, the zwitterionic polymer is interpenetrated on the subsurface of the polymer fiber, and the two components form a subsurface double-network interpenetrating structure, so that the zwitterionic polymer is firmly combined on the polymer fiber through a spatial structure. The invention endows the polymer fiber with the functions of lubricating and preventing tissue adhesion, and provides a foundation for medical application of the polymer fiber with the micro-nano size.

In some embodiments, the polymer fibers and the zwitterionic polymers are bonded only at sub-surface and surface locations.

In some embodiments, the polymer fibers have diameters on the nanometer or micrometer scale. Fibers are often referred to as "fine fibers," which include fibers having micron-scale diameters (i.e., fibers having a diameter of at least 1 micron) and fibers having nanometer-scale diameters (i.e., fibers having a diameter of less than 1 micron). The fibers may be of any size and shape, and are typically cylindrical. Typically, the polymer fibers have a diameter of 0.01 to 100, more typically 0.05 to 10, and most typically 0.1 to 1 micron. In various embodiments, the diameter of the polymer fiber is 1 nm-30 μm, 1-500 nm, 1-100 nm, 100-300 nm, 100-500 nm, 50-400 nm, 300-600 nm, 400-700 nm, 500-800 nm, 500-1000 nm, 1500-3000 nm, 1000-5000 nm, 2000-5000 nm, or 3000-4000 nm. The polymer fibers also typically have a size of 5-20 microns, and more typically have a size of 10-15 microns. However, the polymer fibers are not limited to any particular size.

The polymer fibers may also be attached to each other by any means known in the art. For example, the polymer fibers may be fused together where they overlap or may be physically separated such that the polymer fibers merely lay on each other within the article. It is believed that the polymer fibers, when joined, can form a web or mat having a pore size of 0.01 to 100 microns. In various embodiments, the pore size ranges from 0.1 to 100, 0.1 to 50, 0.1 to 10, 0.1 to 5, 0.1 to 2, or 0.1 to 1.5 microns in size. It is to be understood that the porosity may be uniform or non-uniform. That is, the fibrous article may include different regions having different porosity within a region or between regions. Further, the polymer fibers can have any cross-sectional feature including, but not limited to, a ribbon-like cross-sectional feature, an elliptical cross-sectional feature, a circular cross-sectional feature, and combinations thereof. In some embodiments, "beading" of the polymer fibers may be observed, which is acceptable for most applications.

The fibrous article may comprise a single layer of polymeric fibers or multiple layers of polymeric fibers. As such, the thickness of the fibrous article may be at least 0.01 microns. More typically, the article has a thickness of from about 1 micron to about 100 microns, and most typically a thickness of from about 25 microns to about 100 microns. The article is not limited to any particular number of fiber plies. The article may be woven or non-woven, and may exhibit microphase separation. In one embodiment, the fibers and articles are non-woven, and the articles are further defined as mats. In another embodiment, the fibers and article are non-woven, and the article is further defined as a web. Alternatively, the article may be a film.

In some embodiments, the polymeric fiber or fiber article can be made by electrospinning.

Electrospinning, also known in the art as electrospinning, includes a charged polymer that moves toward a charged or grounded surface. Fibers produced by electrospinning can have submicron or "nanometer" diameters.

Electrospun polymer fibers may be obtained from a melt, solution or dispersion. For example, a melt, solution or dispersion may be discharged through a small charged orifice (such as a needle) toward a target, where the needle and target have opposite charges. The target (also sometimes referred to as a collector) includes a collection surface, which may be made of various materials and have various shapes, as will be understood by those skilled in the art. When an electrical potential is placed across the melt, solution or dispersion, one or more jets may be formed from which the fiber is drawn as the charge attempts to move toward the ground plane (i.e., target or collector). The needles or orifices typically form a single jet, which can produce fibers at a rate of about 0.1 g/hr. The long fibers produced by this process have fiber diameters in the micron to submicron range. When the fibers are allowed to accumulate on the collection surface, they form a nonwoven fabric (also referred to as a mat).

When the polymer formulation (electrospinning solution) is subjected to an electric field, a taylor cone is formed at the electrospinning needle and the electrospinning jet needles of the polymer formulation are ejected towards a grounded or oppositely charged collector to form solid polymer filaments which are deposited to form the nonwoven material.

In some embodiments, the material of the polymeric fibers is selected from any one or more of the following electrospinnable compounds or polymers thereof: dextran, chitosan, polyvinylpyridine, cellulose ether, hydrolyzed polyacrylamide, polyacrylate, polycarboxylate, polyethylene oxide, polyethyleneimine, polyacrylic acid, polymethacrylic acid, hydroxypropylcellulose, cellulose acetate, cellulose nitrate, algin salt, pullulan, xanthan gum, polyurethane polystyrene, polymethacrylate, polyvinylidene fluoride, perfluoroalkoxy, fluorinated ethylene propylene, polytetrafluoroethylene, polyacrylonitrile, nylon, polycarbonate, polyethylene terephthalate, polyester, polyamide, polyamic acid, polyimide, polylactic acid, polyglycolic acid, polyvinyl chloride, polycaprolactone, polyaniline.

The molecular chain of the zwitter-ion group has both cation and anion groups, and can combine a large number of free water molecules to form a hydration layer. Due to the formation of the hydration layer, the zwitterionic compound has better lubricity. The zwitterionic compound has excellent biocompatibility, the molecular chain of the zwitterionic compound contains an anionic group and a cationic group which have the same total number of positive charges and negative charges, the hydration layer is formed by the solvation effect and the hydrogen bond effect of the charged terminal functional group, and the hydration layer has various effects such as lubrication and the like. Zwitterionic compounds useful in forming the zwitterionic polymers include phosphorylcholine-type, sulfobetaine-type, and carboxybetaine-type compounds.

In some embodiments, the zwitterionic polymer is polymerized from one or more of 2-Methacryloyloxyethyl Phosphorylcholine (MPC), 3- [ [2- (methacryloyloxy) ethyl ] dimethylammonium ] propionate (CBMA), 3- [ N, N-Dimethyl- [2- (2-methylprop-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonate inner salt (3- [ Dimethyl- [2- (2-methylprop-2-enoyloxy) ethyl ] azanium ] propane-1-sulfonate, SPE), and the base betaine (SBMA).

The invention adopts an electrostatic spinning method to obtain the polymer fiber, and the inventor controls the mass ratio of the compound capable of electrostatic spinning to the initiator to be 100: (0.5-5) automatically distributing an initiator to the subsurface of a single polymer fiber obtained by electrostatic spinning, and then initiating the polymerization reaction of a zwitterionic compound under the initiation condition of a proper initiator to enable the zwitterionic polymer to be inserted on the subsurface of the polymer fiber, so that the two components form a subsurface dual-network interpenetrating structure. The results show that the method not only does not damage the size structure of the polymer fiber, but also enables the zwitterionic polymer to be firmly bonded on the polymer fiber through a spatial structure. The fiber product prepared by the method keeps the micro-nano size of the polymer of electrostatic spinning, endows the polymer fiber with the functions of lubricating and preventing tissue adhesion, and provides a foundation for the medical application of the polymer fiber with the micro-nano size.

In some embodiments, the initiator is selected from photopolymerization initiators, and the initiation condition is ultraviolet light irradiation.

Electrospinning is a common method that involves the use of electrostatic charges to form a fibrous mat. Typically, electrospinning involves loading an electrospinning solution into a syringe and driving the solution with a syringe pump to the tip of the syringe where droplets are formed. Electrospinning also typically involves applying a voltage to the needles to form a charged jet of solution. The jet was then extended and the thread was continuously rubbed by electrostatic repulsion until it was deposited on a grounded collector, forming a fibrous mat.

The electrospinning solution comprises a liquid and a curable compound (an electrospinning compound). The method includes the steps of forming an electrospinning solution and electrospinning the electrospinning solution. In one embodiment, the method includes the step of solidifying the electrospinnable compound.

The polymer fibers can be formed from an electrospun compound. In the present invention, the electrospinning solution includes a solvent, an initiator, and a curable compound (an electrospinning compound), as described in more detail below. In electrospinning, the solvent may be a non-polar liquid. The solvent may be a polar liquid, such as an alcohol, an ionic liquid, or water. Typically, the solvent is an alcohol. In one embodiment, the electrospinning solution composition includes solid electrospinning compound particles and a solvent in the form of a continuous phase. In various embodiments, the solvent may be present in an amount of 10% to 90% by mass of the electrospinning solution, for example 10, 20, 30, 40, 50, 60, 70, 80, 90 parts by weight relative to 100 parts by weight of the electrospinning solution.

The electrospinning solution also includes an electrospinning compound. The electrospun compound may be any organic compound known in the art that is electrospun curable. Examples of such electrospinnable compounds include, but are not limited to, peroxides, amides, acrylates, esters, ethers, imides, oxiranes, sulfones, ureas, urethanes, compounds having ethylenic unsaturation, and combinations thereof. In various embodiments, the mass to volume ratio of the electrospinnable compound (mass) to the solvent (volume) can be (10-20): 100, e.g., 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 parts by weight (g) relative to 100 volumes (ml) of solvent.

In the photocuring system, molecules receive or absorb external energy and then undergo chemical changes to decompose into free radicals or cations, so that the polymerization reaction is initiated. The photopolymerization initiator is generally referred to as a photopolymerization initiator, and any substance which can generate radicals and further initiate polymerization when irradiated with light. The photopolymerization initiator (also called photosensitizer) or photocuring agent (photocuring agent) is a compound which can absorb energy with a certain wavelength in an ultraviolet region (250-420 nm) or a visible light region (400-800 nm) to generate free radicals, cations and the like so as to initiate the polymerization, crosslinking and curing of monomers.

As the photopolymerization initiator, a compound that generates radical active species by ultraviolet rays or the like is preferable. Specifically, there may be mentioned: benzoin alkyl ether initiators such as benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether and benzoin isobutyl ether, benzophenone initiators such as benzophenone, benzoylbenzoic acid, 3 '-dimethyl-4-methoxybenzophenone and polyvinyl benzophenone, aromatic ketone initiators such as α -hydroxycyclohexylphenyl ketone, 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, α -hydroxy- α, α' -dimethylacetophenone, methoxyacetophenone, 2-dimethoxy-2-phenylacetophenone, 2-diethoxyacetophenone and 2-methyl-1- [4- (methylthio) -phenyl ] -2-morpholinopropan-1-one, aromatic ketal initiators such as benzyl dimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-dodecylthioxanthone, 2, 4-dichlorothioxanthone, 2, 4-dimethylthioxanthone, 2, 4-diethylthioxanthone, 2, 4-diisopropylthioxanthone, benzil initiators such as benzil, benzoin initiators such as benzoin, alpha-ketol compounds such as 2-methyl-2-hydroxypropiophenone, aromatic sulfonyl chloride compounds such as 2-naphthalenesulfonyl chloride, optically active oxime compounds such as 1-phenone-1, 1-propanedione-2- (m-ethoxycarbonyl) oxime, camphorquinone compounds, halogenated ketone compounds, acylphosphine oxide compounds, and acylphosphonate compounds. These may be used alone, or two or more of them may be used in combination.

As the photopolymerization initiator, commercially available products can be used. Specific examples thereof include IRGACURE 184, IRGACURE 127, DAROCUR 1173, IRGACURE 2959, IRGACURE 500, IRGACURE 369, IRGACURE 907, IRGACURE 651, IRGACURE 250, IRGACURE 819, and LUCIRIN TPO. Preferably, the photopolymerization initiator is selected from IRGACURE 2959, and hydroxyl functional groups in the molecule enhance the solubility of IRGACURE 2959 in aqueous coating formulations. IRGACURE 2959 has lower volatility and odor than IRGACURE 1173. Importantly, the active hydroxyl groups of IRGACURE 2959 are easily grafted onto the polymer molecule, making it more convenient to process.

The inventor finds that the proportion of the electrostatic spinning compound and the initiator plays an important role in the automatic arrangement of the initiator on the sub-surface of the polymer fiber in the electrostatic spinning process. In some embodiments, the mass ratio of electrospinning compound to initiator is 100: (0.5-5). For example 100: 0.5, 100: 1. 100, and (2) a step of: 1.5, 100: 2. 100, and (2) a step of: 2.5, 100: 3. 100, and (2) a step of: 3.5, 100: 4. 100, and (2) a step of: 4.5, 100: 5. in a specific embodiment, the electrospinnable compound is selected from polylactic acid, the initiator is selected from IRGACURE 2959, and the mass ratio of the polylactic acid to the initiator in the electrospinning solution is 100: (0.5-5). Preferably, the mass ratio of the polylactic acid to the initiator in the electrospinning solution is 100: (0.8 to 1.2). Under the proportion, the initiator can be better and automatically distributed on the subsurface of the electrostatic spinning polymer fiber.

The method includes the step of forming an electrospinning solution as described above. The electrospinning solution may be formed by adding the solvent, initiator, and electrospinnable compound together or separately and mixing. The mixing step can include mechanical mixing using ribbon mixers, plow mixers, fluidized paddle mixers, sigma (sigma) blade mixers, tumble blenders, vortex mixers, raw material mixers, vertical mixers, horizontal mixers, rotor-stator mixers, sonicators, and combinations thereof.

Without intending to be bound by any particular theory, it is believed that electrospinning causes at least partial evaporation of a liquid, such as a solvent, and as a result, curing of the cured compound may be condensed. Loss of solvent may allow the electrospun compounds to blend, i.e., come into intimate contact, allowing for curing. Without intending to be bound by any particular theory, it is believed that the electric forces used in electrospinning can calibrate the functional groups so that they are more easily accessible. The electrospinning step can be carried out by any method known in the art. Typical electrospinning processes include the use of electrical charges to form fibers. Typically, the electrospinning solution used to form the fibers is loaded into a syringe, the electrospinning solution is driven to the tip of the syringe using a syringe pump, and droplets are formed at the tip of the syringe. The pump controls the flow of the electrospinning solution used to form the fibers to the spinneret. The flow rate of the electrospinning solution used to form the fibers through the tip of the syringe can have an effect on the formation of the fibers. The flow rate of the electrospinning solution through the tip of the syringe (i.e., the advancing speed of the electrospinning solution) may be from about 4ml/h to about 8ml/h, typically from about 4ml/h, 4.5ml/h, 5ml/h, 5.5ml/h, 6ml/h, 6.5ml/h, 7ml/h, 7.5ml/h, 8ml/h, more typically from about 5ml/h to about 7 ml/h. In a specific embodiment, the flow rate of the electrospinning solution through the syringe tip may be about 6 ml/h.

The droplets are then typically exposed to a high voltage electric field. In the absence of a high voltage electric field, the droplet leaves the tip of the syringe in an 1/4 spherical shape, which is a result of the surface tension inside the droplet. Application of an electric field causes the sphere to deform into a cone. This distortion of the droplet shape is generally accepted to explain that the surface tension within the droplet is neutralized by the electrical forces. A narrow diameter jet of electrospinning solution flows out of the cone tip. Under some process conditions, the jet of electrospinning solution experiences a "twisting" instability phenomenon. This thread-twisting instability leads to repeated bifurcations of the jet, resulting in a fiber network. The fibers are finally collected on a collector plate. It is believed that during the electrospinning process, a liquid, such as a solvent, rapidly evaporates from the electrospinning solution, leaving a solid portion of the electrospinning solution, forming fibers, and solidifying the electrospinnable compound. The collector plate is typically formed from a solid conductive material such as, but not limited to, aluminum, steel, nickel alloys, silicon wafers, fabrics, and cellulose (e.g., paper). During electrospinning, the collector plate acts as a ground source for the passage of electrical current through the fibers. Over time, the amount of polymeric fibers collected on the collector plate increases and a nonwoven fibrous mat is formed on the collector plate. Alternatively, instead of using a collection plate, the fibers can be collected on the surface of a liquid that is not part of the electrospinning solution, thereby achieving a free-standing nonwoven mat. One example of a liquid that can be used to collect the fibers is water.

In various embodiments, the electrospinning step comprises supplying electricity from a DC generator having a power generating capacity of about 10 to about 100 Kilovolts (KV). In particular, the injector is electrically connected to the generator. The step of exposing the droplets to a high voltage electric field typically comprises applying a voltage and current to the injector. The applied voltage may be from about 5KV to about 100KV, typically from about 10KV to about 40KV, more typically from about 15KV to about 35KV, and most typically from about 20KV to 30 KV. In one particular example, the applied voltage may be about 20 KV. The applied current can be from about 0.01nA to about 100,000nA, typically from about 10nA to about 1000nA, more typically from about 50nA to about 500nA, and most typically from about 75nA to about 100 nA. In a specific embodiment, the current is about 85 nA. Typically, when electrospinning, the electrospinning solution is at a temperature within 60 ℃ of ambient temperature. More typically, when electrospinning, the electrospinning solution is at a temperature within 60 ℃ of the processing temperature.

In some embodiments, other parameter conditions for electrospinning are: the receiving distance is 17 cm-19 cm.

In some embodiments, the wavelength of the ultraviolet light irradiation is 360nm to 370nm, and the irradiation time of the single-sided polymer fiber may be 40min to 60 min.

Example 1

The detailed steps are as follows:

(1) firstly, preparing a mixed solution of levorotatory polylactic acid (PDLLA) (with the mass-average molecular weight of 8.7 ten thousand) and I-2959, wherein the solvent is hexafluoroisopropanol. If the solvent is 20mL, PDLLA will constitute 12% (w/v) of the solvent, i.e., 2.4g, while I-2959 will constitute 1% (w/w) of PDLLA. And stirring the mixture overnight at normal temperature by using a stirrer during dissolving to obtain a clear electrostatic spinning solution.

(2) The electrospinning solution is subjected to an electrospinning process. The parameters of electrostatic spinning are adjusted as follows: the voltage is 20kV, the receiving distance is 18cm, the solution advancing speed is 6mL/h, and the solution is received by a roller at normal temperature and normal pressure. After spinning is finished, the fiber film is carefully torn off and placed in a cool and dry place for storage for more than one week for later use.

(3) And (4) preparing the coating. And (3) taking down a 6cm by 6cm fiber membrane, putting the fiber membrane into a transparent glass culture dish, pouring 30mL of MPC solution (with the concentration of 10% w/v and the solvent of deionized water), respectively irradiating the front side and the back side for 50min under the ultraviolet light with the wavelength of 365nm, immediately washing the front side and the back side for at least 10 times by using a large amount of deionized water, washing away unreacted monomer MPC on the surface, and naturally drying.

The coefficient of friction of the fiber membranes was tested using the UMT-5 spin mode with coefficient of friction data as: the friction coefficient of the coated fibrous membrane obtained in the step (3) was 0.02. The uncoated fibrous membrane obtained in step (2) had a coefficient of friction of 0.4.

The SEM and XPS images of the uncoated fibrous film obtained in step (2) of this example are shown in FIGS. 1A-1B and 1E, respectively. The electron micrograph and XPS chart of the coated fiber film obtained in step (3) are shown in FIGS. 1C-1D and 1F, respectively. The electron micrograph shows that the structure of the coated nanofiber is not damaged and basically keeps the original appearance. XPS plots indicate the incorporation of PMPC on the nanofiber membrane.

The coated fibrous membrane prepared in this example was attached between the abdominal cavity and the intestinal wall. As shown in fig. 3B, there is no adhesion between the abdominal cavity and the intestinal wall. Fig. 3A does not provide a fibrous membrane between the abdominal cavity and the intestinal wall. As shown in fig. 3A and 3B, compared with the control without the membrane, it was found that severe tissue adhesion of abdominal cavity and intestinal wall occurred in the control group, whereas no tissue adhesion occurred in the present example.

Comparative example

Firstly, soaking PLA nano-fibers prepared by electrostatic spinning in a solution of a hydrophobic photoinitiator BP for 5min to realize permeation of BP on the sub-surface of the fibers, and then putting the fibers into an aqueous solution of MPC/I-2959 to carry out UV ultraviolet initiation. Electron micrographs and XPS images of PLA nanofibers that were not soaked with hydrophobic photoinitiator BP are shown in figures 2A-2B and 2E, respectively. Electron micrographs and XPS images of PLA nanofibers after uv illumination are shown in figures 2C-2D and 2F, respectively. As can be seen from the electron micrographs and XPS images, while PMPC coatings can be obtained by this method, the structure of the nanofibers has been destroyed.

Example 2

The influence of the use concentration of the initiator on the structure and function of the fiber membrane was investigated in exactly the same manner as in example 1, and the PMPC binding amount (content of P element) on the finally obtained coated fiber membrane was used as a characterizing parameter. Setting initiator concentration as I-2959 accounts for 0%, 0.5%, 1%, 5%, 10% and (w/w) of PDLLA. The results are shown in Table 1. The results show that the initiator can be automatically arranged on the sub-surface of the polymer fiber when the concentration of I-2959 accounts for 1 percent of the PDLLA, so that the zwitterionic polymer can be more bonded on the polymer fiber.

TABLE 1

Content of I-2959	Content of P element
		0％	0.36％
0.5％	0.91％
		1％	1.13％
5％	0.66％
		10％	0.6％

The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.

The above-mentioned embodiments only express several embodiments of the present invention, so as to understand the technical solutions of the present invention specifically and in detail, but not to be understood as the limitation of the patent protection scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the patent of the invention is subject to the appended claims, and the description can be used for explaining the contents of the claims.

Claims

1. A fibrous article comprising a polymer fiber and a zwitterionic polymer bonded to a subsurface of said polymer fiber and to a surface of said polymer fiber, said polymer fiber and said zwitterionic polymer forming a bi-network interpenetrating structure, said polymer fiber subsurface being located at a nanoscale dimension from an outer surface of said polymer fiber.

2. A fibrous article according to claim 1, wherein said polymeric fibers have a diameter in the nanometer or micrometer range.

3. A fibrous product according to claim 1, characterized in that said fibrous product is a web or a mat.

4. A fibrous article according to claim 1, wherein said polymeric fibres are of a material selected from any one or more of the following electrospun compounds or polymers thereof: dextran, chitosan, polyvinylpyridine, cellulose ether, hydrolyzed polyacrylamide, polyacrylate, polycarboxylate, polyethylene oxide, polyethyleneimine, polyacrylic acid, polymethacrylic acid, hydroxypropylcellulose, cellulose acetate, cellulose nitrate, algin salt, pullulan, xanthan gum, polyurethane polystyrene, polymethacrylate, polyvinylidene fluoride, perfluoroalkoxy, fluorinated ethylene propylene, polytetrafluoroethylene, polyacrylonitrile, nylon, polycarbonate, polyethylene terephthalate, polyester, polyamide, polyamic acid, polyimide, polylactic acid, polyglycolic acid, polyvinyl chloride, polycaprolactone, polyaniline.

5. A fibrous article according to claim 1, wherein said zwitterionic polymer is derived from the polymerization of one or more of 2-methacryloyloxyethyl phosphorylcholine, 3- [ [2- (methacryloyloxy) ethyl ] dimethylammonium ] propionate, 3- [ N, N-dimethyl- [2- (2-methylprop-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonic acid inner salt and the base betaine.

6. A method of making a fibrous product according to any of claims 1 to 5, comprising the steps of:

7. A method for producing a fibrous product according to claim 6, wherein said initiator is selected from photopolymerization initiators, and said initiation condition is ultraviolet irradiation.

8. The method of producing a fiber product according to claim 7, wherein the photopolymerization initiator is one or more selected from the group consisting of a benzoin alkyl ether initiator, a benzophenone initiator, an aromatic ketone initiator, an aromatic ketal initiator, a thioxanthone initiator, a benzil initiator, a benzoin initiator, an α -ketol compound, an aromatic sulfonyl chloride compound, a photoactive oxime compound, a camphorquinone compound, a halogenated ketone compound, an acylphosphine oxide compound, and an acylphosphonate compound; and/or, the photopolymerization initiator is selected from any one or more of IRGACURE 184, IRGACURE 127, DAROCUR 1173, IRGACURE 2959, IRGACURE 500, IRGACURE 369, IRGACURE 907, IRGACURE 651, IRGACURE 250, IRGACURE 819 and LUCIRIN TPO.

9. The method of claim 6, wherein the electrospinnable compound is selected from polylactic acid, the initiator is selected from IRGACURE 2959, and the mass ratio of polylactic acid to IRGACURE 2959 is 100: (0.8 to 1.2).

10. A method of producing a fibrous product according to any of claims 6 to 9, characterized in that the electrospinning has the parameter conditions: the voltage is 18kV to 22kV, the receiving distance is 17cm to 19cm, and the solution advancing speed is 5.5mL/h to 6.5 mL/h.